This invention relates to a process for the production of polyester resinous products by chemically reacting an organic epoxide compound, an oxidated silicon compound and a polycarboxylic acid and/or a polycarboxylic acid anhydride.
The polyester resinous products may be utilized as a protective coating for wood, metal, plastic, linoleum, leather, fabric and rubber. They may be utilized in paints, lacquers, metal primers, caulking compounds and water-emulsion paints. The unsaturated polyester silicate resinous products, when copolymerized with a polymerizable organic compound, will produce hard, solid, useful objects or they may be used in conjunction with a reinforcing filler such as fiberglas fibers or cloth, paper, wire mesh, etc., to produce a laminate of outstanding strength and durability. They may also be used as a molding powder, as an adhesive and as impregnants. These resinous products may be further reacted with epihalohydrins and polyisocyanate compounds to produce resinous products and foam.
Polyester silicate resinous products may be modified with vegetable oils, vinyl monomers, aminoplasts, phenoplasts, phenol, melamine, silicone resins, silicone silicate resins, cellulose nitrate, cellulose, polyisocyanates, cyclopentadienes, terpenes, mono-basic acids, e.g., benzoic acid and p-tert-butyl benzoic acid; they may be modified with natural resins, ethyl cellulose, chlorinated rubber, aldehyde phenol silicate resins, aldehydes, polyhydroxy compounds and other synthetic and modified natural resins. An excess of hydrated silica may be used to modify the polyester silicate resinous products by making the resin more solvent-resistant and improving its physical strength.
Polyester silicate resinous products may be produced by reacting the following components:
(a) an oxidated silicon compound; PA1 (b) an organic epoxide compound; PA1 (c) a polycarboxylic acid, a polycarboxylic acid anhydride and mixtures thereof; PA1 (d) a Lewis acid. PA1 p-benzo-quinone, PA1 2,5-dichlorobenzoquinone, PA1 2,6-dichlorobenzoquinone, PA1 chloranil, PA1 naphthoquinone-(1,4), PA1 anthraquinone, PA1 2-methylanthraquinone, PA1 1,4-dimethylanthraquinone, PA1 1-chloroanthraquinone, PA1 anthraquinone-2-carboxylic acid, PA1 1,5-dichloroanthraquinone, PA1 1-chloro-4-nitroanthraquinone, PA1 phenanthrene-quinone, PA1 acenaphenequinone, PA1 pyranthrenequinone, PA1 chrysenequinone, PA1 thio-naphthene-quinone, PA1 anthraquinone-1,8-disulfonic acid and anthraquinone-2-aldehyde; PA1 bromal, PA1 4-nitrobenzaldehyde, PA1 2,6-dichlorobenzaldehyde-2, PA1 ethoxy-1-naphthalidehyde, PA1 anthracene-9-aldehyde, PA1 pyrene-3-aldehyde, PA1 oxindole-3-aldehyde, PA1 pyridine-2,6-dialdehyde, PA1 biphenyl-4-aldehyde; PA1 4-chloro-2-nitrobenzene-phosphonic acid nitrophenols, such as 4-nitrophenol, PA1 picric acid; PA1 acetic-anhydride, PA1 succinic anhydride, PA1 maleic anhydride, PA1 phthalic anhydride, PA1 tetrachlorophthalic anhydride, PA1 perylene-3,4,9,10-tetracarboxylic acid and PA1 chrysene-2,3-8,9-tetracarboxylic anhydride, PA1 di-bromo maleic acid anhydride; PA1 aluminum chloride, PA1 zinc chloride, PA1 ferric chloride, PA1 tin tetrachloride, PA1 (stannic chloride), PA1 arsenic trichloride, PA1 stannous chloride, PA1 antimony pentachloride, PA1 magnesium chloride, PA1 magnesium bromide, PA1 calcium bromide, PA1 calcium iodide, PA1 strontium bromide, PA1 chromic bromide, PA1 manganous chloride, PA1 cobaltous chloride, PA1 cobaltic chloride, PA1 cupric bromide, PA1 ceric chloride, PA1 thorium chloride, PA1 arsenic tri-iodide; PA1 boron trifluoride, PA1 boron trichloride; PA1 acetophenone, PA1 benzophenone, PA1 2-acetylnaphthalene, PA1 benzil, PA1 benzoin, PA1 5-benzoylacenaphthene, PA1 biacene-dione, PA1 9-acetyl-anthracene, PA1 9-benzoyl-anthracene, PA1 4-(4-dimethyl-amino-cinnamoyl)-1-acetylbenzene, PA1 acetoacetic acid anilide, PA1 indandione-(1,3), PA1 (1,3-diketohydrindene), PA1 acenaphthene quinone-dichloride, PA1 anisil, PA1 2,2-puridil and PA1 furil. PA1 the hydrogen halides, PA1 sulphuric acid and PA1 phosphoric acid; PA1 acetic acid and the substitution products thereof, PA1 monochloro-acetic acid, PA1 dichloroacetic acid, PA1 trichloroacetic acid, PA1 phenylacetic acid, PA1 7-methylcoumarinylacetic acid (4), PA1 maleic acid, PA1 cinnamic acid, PA1 benzoic acid, PA1 1-(4-diethyl-amino-benzoyl)-benzene-2-carboxylic acid, PA1 phthalic acid, PA1 and tetra-chlorophthalic acid, PA1 alpha-beta-dibromo-beta-formyl-acrylic acid (mucobromic acid), PA1 dibromo-maleic acid, PA1 2-bromo-benzoic acid, PA1 gallic acid, PA1 3-nitro-2-hydroxy-1-benzoic acid, PA1 2-nitro phenoxy-acetic acid, PA1 2-nitro-benzoic acid, PA1 3-nitro-benzoic acid, PA1 4-nitro-benzoic acid, PA1 2-chloro-4-nitro-1-benzoic acid, PA1 3-nitro-4-methoxy-benzoic acid, PA1 4-nitro-1-methyl-benzoic acid, PA1 2-chloro-5-nitro-1-benzoic acid, PA1 3-chloro-6-nitro-1-benzoic acid, PA1 4-chloro-3-nitro-1-benzoic acid, PA1 5-chloro-3-nitro-2-hydroxybenzoic acid, PA1 4-chloro-1-hydroxy-benzoic acid, PA1 2,4-dinitro-1-benzoic acid, PA1 2-bromo-5-nitro benzoic acid, PA1 4-chlorophenyl-acetic acid, PA1 2-chloro-cinnamic acid, PA1 2-cyana-cinnamic acid, PA1 2,4-dichlorobenzoic acid, PA1 3,5-dinitro-benzoic acid, PA1 3,5-nitro-salycylic acid, PA1 malonic acid, PA1 mucic acid, PA1 acetosalycylic acid, PA1 benzilic acid, PA1 butane-tetra-carboxylic acid, PA1 citric acid, PA1 cyano-acetic acid, PA1 cyclo-hexane-dicarboxylic acid, PA1 cyclo-hexane-carboxylic acid, PA1 1,10-dichlorostearic acid, PA1 fumaric acid, PA1 itaconic acid, PA1 levulinic acid, PA1 (levulic acid), PA1 malic acid, PA1 succinic acid, PA1 alpha-bromo stearic acid, PA1 citraconic acid, PA1 dibromo-succinic acid, PA1 pyrene-2,3,7,8-tetra-carboxylic acid, PA1 tartaric acid; PA1 4-toluene sulphonic acid, and benzene sulphonic acid, PA1 2,4-dinitro-1-methyl-benzene-6-sulphonic acid, PA1 2,6-dinitro-1-hydroxy-benzene-4-sulphonic acid, PA1 2-nitro-1-hydroxy-benzene-4-sulphonic acid, PA1 4-nitro-1-hydroxy-2-benzene-sulphonic acid, PA1 3-nitro-2-methyl-1-hydroxy-benzene-5-sulphonic acid, PA1 6-nitro-4-methyl-1-hydroxy-benzene-2-sulphonic acid, PA1 4-chloro-1-hydroxy-benzene-3-sulphonic acid, PA1 2-chloro-3-nitro-1-methyl-benzene-5-sulphonic acid and PA1 2-chloro-1-methyl-benzene-4-sulphonic acid. PA1 1-cyclohexylamine-3-aminopropane; PA1 1,4-diaminocyclohexane; PA1 1,3-diaminocyclopentane; PA1 di(aminocyclohexyl) methane; PA1 di(aminocyclohexyl) sulfone; PA1 1,3-di(aminocyclohexyl) propane; PA1 2,4-diaminocyclohexane; PA1 N,N'-diethyl-1,4-diaminocyclohexane, and the like. PA1 N-(3-butylthio-2-hydroxypropyl) triethylenetetramine, PA1 N-(4-phenylthio-3-hydrobutyl) pentamethylenetetramine, PA1 N-(4-cyclohexylthio-3-hydrobutyl) ethylenediamine, PA1 N-(4-cyclohexylthio-3-hydrobutyl) ethylenediamine, PA1 N-(3-cyclohexylthio-2-hydropropyl) hexamethylenediamine, PA1 N-(3-diphenylphosphino-2-hydroxypropyl) triethylenetetramine, PA1 N-(3-dicyclohelylphosphino-2-hydroxpropyl) pentamethylenetetramine, PA1 N-(3-dididecylphosphino-2-hydroxylhexyl) diethylenetriamine, and PA1 N-(3-allylthio-2-hydroxypropyl) hexamethylenediamine. PA1 tolylene diisocyanate, PA1 p,p'-diphenylmethane diisocyanate, PA1 phenylene diisocyanate, PA1 m-xylylene diisocyanate, PA1 chlorophenylene diisocyanate, PA1 benzidene diisocyanate, PA1 naphthylene diisocyanate, PA1 decamethylene diisocyanate, PA1 hexamethylene diisocyanate, PA1 pentamethylene diisocyanate, PA1 tetramethylene diisocyanate, PA1 thiodipropyl diisocyanate, PA1 propylene diisocyanate, and PA1 ethylene diisocyanate. PA1 1. Water. PA1 2. Water containing 10% to 70% by weight of an alkali metal silicate, such as sodium and/or potassium silicate. Crude commercial alkali metal silicate may contain other substances, e.g., calcium silicate, magnesium silicate, borates or aluminates and may also be used. The molar ratio of alkali metal oxide to SiO.sub.2 is not critical and may vary within the usual limits, but is preferably between 4 to 1 and 0.2 to 1. PA1 3. Water containing 20% to 50% by weight of ammonium silicate. PA1 4. Water containing 5% to 40% by weight of magnesium oxide in the form of a colloidal dispersion. PA1 5. Alkali metal metasilicate such as sodium metasilicate, potassium metasilicate and commercial dry granular sodium and potassium silicates. Heating may be required to start the curing reaction. PA1 6. Water containing 20% to 70% by weight of silica sol. PA1 7. Activators (catalysts) which act as curing agents and are added to the polyurethane or polyurethane prepolymer in the amount of 0.001% to 10% by weight. They may be added in water. PA1 8. Water containing 1% to 10% by weight of bases which contain nitrogen such as tetraalkyl ammonium hydroxides. PA1 9. Water containing 1% to 10% by weight of alkali metal hydroxides such as sodium hydroxide; alkali metal phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. PA1 10. Water containing sodium polysulfide in the amount of 1% to 10% by weight. PA1 11. Water containing 20% to 70% by weight of a water-binding agent, being capable of absorbing water to form a solid or a gel, such as hydraulic cement, synthetic anhydrite, gypsum or burnt lime. PA1 12. Mixtures of the above-named curing agents. Surface-active additives (emulsifiers and foam stabilizers) may also be used according to the invention. Suitable emulsifiers are, e.g., the sodium salts of ricinoleic sulphonates or of fatty acid, or salts of fatty acids with amines, e.g., oleic acid diethylamine or stearic acid diethanolamine. Other surface-active additives are alkali metal or ammonium salts of sulphonic acids, e.g., dodecylbenzine sulphonic acid or dinaphthyl methane disulphonic acid; or of fatty acids, e.g., ricinoleic acid. or of polymeric fatty acids. PA1 (a) 1 to 95 parts by weight of a polyester silicate resinous product, preferably with free hydroxyl group and produced by the process of this invention. PA1 (b) 50 parts by weight of polyisocyanate, polyisocyanate or isocyanate-terminated polyurethane prepolymer; PA1 (c) up to 20% by weight of a foam stabilizer; PA1 (d) up to 50% by weight of a chemically inert blowing agent, boiling within the range of from -25.degree. C. to 80.degree. C.; PA1 (e) up to 10% by weight of an activator; PA1 (f) up to 200 parts by weight of a water-binding agent; PA1 (g) up to 95 parts by weight of a polyol; PA1 (h) up to 5% by weight of an emulsifier; PA1 (i) up to 50% by weight of a curing agent.